Abstract

The structure of hydroxymethyl hydroperoxide (HMHP) has been examined using coupled cluster and multireference configuration interaction methods to study the excited states and probable photodissociation products. The results are compared to experiments. The vertical excitation energies for several excited states of are presented as well as the excited stateenergies along the O–O, O–H, C–O, and C–H dissociation pathways. The results help in the interpretation of experimental UV absorption spectra and elucidate the photodissociation mechanism of HMHP under tropospheric conditions.

Received 17 December 2007Accepted 24 March 2008Published online 05 May 2008

Acknowledgments:

W.E. is grateful to the Leibniz Rechenzentrum Munich for providing large amounts of computer time. We are grateful for the assistance of the Purdue University ITaP for computing resources to complete this project.